Method of clarifying mash



Febl5, 1949. A. J. STROHMALEB Er Al. 1 2,451,933

METHOD oF CLARIF'YING M AH Filed Nov, 1e, 1944.

Fig.1 Fig. a

/.o Percent.l flo/ame) 7vt/o/'e/75/ene ,o h of Mus/7 Fi g. 3 f/ed of Mas/7 Temperature I vClifton L. Lovell BY www@ Patented Feb. 15, 1949 METHOD OF CLARIFYING MASH Alfred J. Strohmaier, Louisville, Ky., and Clifton L; Lovell, West Lafayette, Ind., assignors to ll'oseph E. Seagram & Sons, Inc., Shively, Ky., a corporation of Indiana Application November 16, 1944, Serial No. 563,784

In the manufacture of butadiene, one of the principal ingredients used in the manufacture of the new synthetic elastomers, it has been proposed to ferment an acid hydrolyzed corn mash to a butadiene intermediate, namely 2,3 butanediol. Once a clear eilluent, either in the form of an unfermented mash or a fermented beer', is obtained, it can be easily processed to butadiene. The production of a clear eluent from acid hydrolyzed corn mash and other acid or malt hydrolyzed grain mashes, such as distillery mashes, in a manner sufficiently inexpensive to justify use on a commercial scale, presents a difficult problem.

The present invention relates to this problem and has for its principal object the provision of a' novel and inexpensive solution for it.

Another important object of the invention is to provide a n'ovel method of treating the mash which facilitates its effective clarification by settling or centrifuging operations.

A further important object of the invention is to provide a clarification method which may advantageously be employed prior to fermentation to produce a clear eiliuent capable of being fermented and further processed to butadiene or alcohol, as the case. may be, without further clarification.

Broadly speaking, the invention resides in the discovery that when the mash is treated with a controlled quantity of a relatively heavy wetting solvent, that is to say a solvent having a low surface tension and a high specific gravity, a clear eiiluent may be separated under controlled condition of pH and temperature by centrifuging the treated mash or allowing it to settle. More specifically, the invention comprises treating the mash with a controlled quantity of a halogenated hydrocarbon, of either the aliphatic or aromatic types, adjusting the pH and temperaM ture of the mash to predetermined values and then producing a clear eiuent by a settling or centrifuging operation. While the invention is applicable to grain mashes generally, for the sake of clarity, it is hereinafter specifically described in connection with an acid hydrolyzed uniermented corn mash for butanedol production purposes.

In the drawing:

Figures 1, 2 and 3 are graphs illustrating the eilect, on the ease of clarifying an acid hydrolyzed corn mash for butanediol production purposes, of different amounts of trichlorethylene, of different pH values of the mash. and of dierent temperatures of the mash, respectively.

In carrying out the invention, an acid hydrolyzed corn mash may be prepared, `cooked and hydrolyzed in the customary way. One representative process, which is of a continuous nature, comprises: grinding the corn continu- 15 Claims. (Cl. ZIO-42.5)

ously in a roller mill; continuously mixing the ground corn with Water and sulfuric acid in a slurry tank to form an 0.2 normal suspension; pumping the suspension through a steam jet heater which, by means of pound steam, more or less instantaneously raises the temperature of the suspension to 325 F.; maintaining this temperature by holding the mash under pressure'for 5 minutes in a holding vessel; neutralizing the resulting cook with calcium carbonate; and cooling the neutralized ycook first to a temperature corresponding to atmospheric pressure by discharging it into a flash cooler at atmospheric pressure and second to some desired lower temperature by passing it through a heat exchanger. The conversion of starches to fermentable sugar is virtually complete by the time the material is discharged from the heat exchanger. During the performance of the process, the rates of flow of the corn, Water and steam are so adjusted as to produce a 40 to 44 gallon-per-bushel mash. This results in a dissolved sugar content of approximately 10% with the suspended solids content totaling 1.'7 to 2.2%.

In accordance with `our invention a controlled quantity of a halogenated aliphatic or aromatic hydrocarbon is added to the mash. The hydrocarbon may be halogenated with fluorine, chlorine, bromine or iodine which, in the order named, range from light to heavy. Where weight alone is the determining factor, the heavier halogens or large numbers of the lighter halogens per hydrocarbon molecule are naturally preferred. From the standpoint of economy, chlorine and bromine are preferred in the order named since they are the cheapest. Furthermore, While a multitude fof halogenated hydrocarbons may be employed such as hexachlorpropylene, polychlorpropane, tetrachloroethylene, hexachlorbutadiene, carbon tetrachloride, tribromoethylene, and alpha, betadibrom'oethylene, for the sake of clarity, the present invention will be further described with trichloroethylene as the specific treating agent employed.

The amount of 'trichloroethylene preferably is 2% by volume.

from the curve of Figure 1.

and still obtain useful results although 2% is recommended for optimum results.

The pI-I of the mash should be controlled to secure optimum separation as indicated in Figure 2. With trichloroethylene, the optimum pH approximates 6.7. Here again, however, a varia- I ti'onin pH from 6.0 to 7.2 is well `within a Wider range in which useful results are secured. For

pH control an alkali metal compound or alkaline earth metal compound may be employed.

The temperature ofl the mash must likewise be This amount is chosen because, it produces maximum clarification as will be seen. However, it will be appreciated that the amount employed may var-y.`

controlledrl for optimum results e as 1. indicated inA Figure 3J.. With .trichlorethylenethe ,optimum mash temperature at atmospheric pressure is 150 F. 'I'here is a progressive increase in the effectiveness of the separation as the mash temperature progressively rises from roomfternperature up to 150 F. Beginning with:thistemperature,

however, any further increase isaccompanied by' a decrease in effectiveness because-'the treating: agent begins to distill off. Accordingly, it will be appreciated that, if the separation-fis.. effected under vsuper-atmospheric pressure conditions, it will be possible to employ higher mash; temperatures and, with such temperatures, there is every reason, to expect ,even more; effective separation. Temperatures lower than 150 F., for trichloroethylene, may, of course, be employed and useful results vobtained'. Whatever agent is employed, it wil1.usual1y bedesirable to have themash temp erature at apredetermined value just short hof that` at:which, such agent begins to distill oif.

In..applying.the invention to thenormal practice-ofcooking, neutralizing, cooling and fermenting,.the. mash, the, neutralized cook mayconveniently be. cooled` to, the appropriate treating temperature at which time, the pH can be adjusted. With the mash at predetermined values of` pH andtemperature the-predetermined addition`A of the heavy wetting -solvent is incorporated andi thoroughly dispersed. After dispersion, the

mashfmay be permitted to settle or be subjected to. a. centrifuging.. operation. In either event, a clear liquid will be obtained. The particular action which,occurs.is not definitely known but it isprobably dueto the lcombination of low surface tension, excellent .solvent action .and highV specicgravityf Due to the. rsttwocharacteristics, the agent probably displaces the water and corn. oil on the surface and inthe interstices, of the solids. there is an increase in theapparent specic gravity lof the mash particleswhichfinduces.extremely rapid settlingparticularly when subjected to centrifugahaction.. Since the effectiveness of these agents vary with different types of mashes, thepgnlnt.` This obviates drasticI changes Vin the. pH.

andv minimizes. corrosion. diilculties.` encountered wherethe pHof themash is renderedhighly acid.

The invention is applicable to unfermented.

and fermented acid`or malt hydrolyzed corn or grainmashes.. But, as indicated above. tl1e actionof the .heavy .wetting solvents varies Wthdlfferent mash conditions. For example, it is much more effective with unfermented mashes than it is'with a fermented mash orbeer. This maybe seen from Table 1 which deals with the effect of different 'treating agents on each of ,three 150 F.

mashes, namely: mash A, an unfermented acid hydrolyzed-corn mash-dilutedto 90-94 gallons- Byvirtue of the third characteristic,

per-bushelinstead of 1 0-44 gallons-per-bushel andjhaving a pH 'of 5.76 beer. Bj afermented acid hydrolyzed corn beer having a pH of 5.6; and mash C, an unfermented acid hydrolyzed corn mash diluted to 40-44 gallons-per-bushel and having apH of 6.10, this mash being identical to mash A except that it is more concentrated or less diluted and has a higher pH.

The data in Table 1 were obtained by dividing each mash int-o a number of idential samples and processing each sample as follows: place a pair of treated 'or untreated samples, as the case may be,'.in, the opposed graduated centrifuge tubes of a Clay-Adams Senior variable speed centrifuge havingfa radius of 7 inches from the center of the centrifuge to the outer end of each. centrifuge tube and rotate at 2,000 R. P. M. for, periods ranging from ten seconds (10"')`to.sev enty seconds (70") to settle the solids and thus. separate them from the superjacent liquid; decant the superjacentliquids from each centrifuge tube; and measure the-solids content in each `den` canted liquid. To effect a quick measurementwe. placed the decanted. liquid intoV a DeLavalcentrifuge. having a graduated bowl, rotated itat.4 18,000-R. P. M. tosettle the remaining solids, applying full power to the centrifuge for 2 mine utes, allowing it to coast for 20 seconds (20") and bringing to rest in the next 30seconds. (30"), and then read the solid content directly from the graduated bowl in terms of volume per cent. The Clay-Adams centrifuge subjectsy the liquid and solids to a centrifugal force equal to 820v times. gravity, while the DeLaval centrifuge accounts. for a force of 30,000l times gravity and, for the. most part, 'settles all of the remaining` solids. Table 1 follows:

PILOT PLANT CORN MASHES AND BEER Effect of halogenated hydrocarbons on the per Cent suspended solids remazrz'ng in the Superia,- cent liquid after centrifugation at 2000 R. P.' M. in the Clay-Adams test tube centrifuge 10" 20 40 607 70" Chemical treating Agents (2.0% of mash volume) A A A A A none 3. 1.5 .0 .4 .3 hexacblorpropylen 045 03 02 015 0L polychlorpropane l 03 018 018' Olr tetrachloroethylene l 04 025 .02 .01 hexachlorbutadiene.. l 04 .02 .02 02- trichloroethylene 2 04 i 025 .02 f 02; carbon tetrachloride 25 07 03 02 018 B B B` B B none 7. 5 3.5 3 2. 5 hexachlorpropyleue 3. 1. 5 l. 2 2 l 1.2 polychlorpropane 2. 5 1. 2. 1.0 l. 0 l 1.0 tetrachloroethylene l 1. 5 1. 0 1. 5 l. 2 hexachlorbutadien 2. 8 1.5 1.0 1. 8 l; 2 trchloroethylene carbonLtetrachloride 4 1.5 l. 2 l. 5 1. 2

O C C CT C-` none 7 5 v 4 3 tribromocthylene 2 .3 06 035 02. alpha, beta-dibromo-ethylene 2 6 3 .08 06' Table l, with respectto unfermented dilute mash A, for example, indicates that the Clay- Adams centrifuge left 3% solids, by volume, inr the sufperjacent liquid of the untreated mash after. 10` seconds (10") centrifugation at 2,000 R. P. On the Vother hand, when the mash was provided' with. any of the six treating agentslistedand..

otherwise identicallyprocessed, a solids content was left in the -superjacent liquid ranging from 0.045% (or it? of 3%) up to .25% (or 1/12 of 3%). Where the saine mash is centrifuged for periods progressively longer than seconds (10"), the solids content in untreated mash progressively decreases while the solids content in treated mash likewise progressively decreases, the latter remaining at values less than one-twelfth of the former.

The unfermented but more concentrated mash C, produces results similar to mash A when it is centrifuged for intervals longer than 10 seconds The solids content of the fermented mash B is consistently reduced by the treatment, but the results here are not as pronounced as they are where the mash is unfermented.

It wiil be appreciated that the specific gravity of the hydrocarbon clarifying agent must be greater than water if it is to displace water and thereby increase the apparent specic gravity of the mash solids. Also, since the effectiveness of the clarifying agent decreases when it begins to distill off from the mash, the operating conditions must be such as to hold the clarifying agent in the liquid phase.

Having described our invention, we claim:

1. A. method of clarifying a hydrolized grain mash solution wherein the rapparent specific gravity of the mash solids is increased to facilitate the mechanical separation of the solids from the liquids, comprising: dispersing in the mash a halogenated hydrocarbon, having a, specic gravity greater than water, to increase the apparent speciiic gravity of the solids under operating conditions in which the halogenated hydrocarbon remains in liquid iform; and thereafter mechanically separating the liquids from the solids.

2. The method of claim 1 wherein the mash is an acid hydrolyzed corn mash.

3. The method of claim l wherein the mash is unfermented.

4. The method of claim 1 wherein the mash is an unfermented acid hydrolyzed corn mash for use in the production of butanediol.

5. The' method of claim 1 wherein the halogenated hydrocarbon is used in an amount approximating 2% by volume.

6. The method of claim 1 wherein the mash is 50 adjusted to a predetermined pH.

7. The method of claim 1 wherein the mash is adjusted before the separating action to a predetermined temperature substantially above room temperature and below the temperature at which the halogenated hydrocarbon begins to distill ofi.

8. The method of claim 1 wherein the mash, prior to the separating action, is adjusted to a predetermined pH and to a predetermined temperature substantially above room temperature. and below the distillation temperature of the halogenated hydrocarbon in the mash.

9. A method of clarifying a hydrolized grain mash solution wherein the apparent specic gravity of the mash solids is increased to facilitate the mechanical separation of the solids from the' 5 liquids, comprising: adjusting the mash to a predetermined pH and to a predetermined temperature; dispersing in the mash a liquid halogenated hydrocarbon, having a specific gravity greater than water, to increase the apparent specic grav- 10 ity of the solids, under operating vconditions in which the hydrocarbon remai-ns in liquid form;

and thereafter separating the liquids from the solids.

l0. rThe method of claim 9 wherein the pI-I is 15 within the range of 6.0 and 7.2.

11. The method of claim 9 wherein the ternperature of the mash is substantially above room temperature and below the distillation temperature of the halogenated hydrocarbon in the mash.

12. The method of claim 9 wherein the volume of the halogenated hydrocarbon approximates 2% of the' volume of the mash.

13. The method of claim 9 wherein the pH is adjusted to the range of 6.0 to 7.2, and the temperature is adjusted to a value substantially above room temperature and below the distillation ternperature of the halogenated hydrocarbon in the mash.

14. The method of claim 9 wherein the pH approximates 6.7, the temperature approximates 150 F., the halogenated hydrocarbon is trichlorethylene in an amount approximating 2% by volume and the mash solids are separated by centrifugal force.

15. A` method of clarifying a grain mash containing dispersed solids which comprises: dispersing in the mash a halogenated hydrocarbon having a specific gravity greater than water, in such proportion and under conditions of temperature 40` and hydrogen ion concentration tov increase the apparent specificgravity of the dispersed solids and maintain the halogenated hydrocarbon in liquid phase; and thereafter separating the solids from the mash.

ALFRED J. STROHMAIER. CLIFTON L. LOVELL.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATESI PATENTS 

